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WO2006048792A1 - Nouveau procede de dimerisation de glyoxals alkyliques - Google Patents

Nouveau procede de dimerisation de glyoxals alkyliques Download PDF

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Publication number
WO2006048792A1
WO2006048792A1 PCT/IB2005/053489 IB2005053489W WO2006048792A1 WO 2006048792 A1 WO2006048792 A1 WO 2006048792A1 IB 2005053489 W IB2005053489 W IB 2005053489W WO 2006048792 A1 WO2006048792 A1 WO 2006048792A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
dimerisation
alkaline
comprised
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2005/053489
Other languages
English (en)
Inventor
Ferdinand Naef
René DECORZANT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Firmenich SA
Original Assignee
Firmenich SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Firmenich SA filed Critical Firmenich SA
Priority to JP2007539665A priority Critical patent/JP2008519027A/ja
Priority to EP05796277A priority patent/EP1812369A1/fr
Publication of WO2006048792A1 publication Critical patent/WO2006048792A1/fr
Priority to US11/692,809 priority patent/US7345206B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/17—Saturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups

Definitions

  • the present invention relates to the field of organic synthesis and more particularly to a new process for the preparation of compounds of formula (I) by the reductive dimerisation of an alkyl glyoxal (II) promoted by an alkaline salt of the hydroxymethanesulfinic acid (HOCH 2 SO 2 M), preferably HOCH 2 SO 2 Na-2H 2 O, according to Scheme (1):
  • Scheme 1 Reductive dimerisation of glyoxals according to the invention
  • R 1 represents simultaneously a linear or branched Ci to C 5 alkyl group, and M is an alkaline metal ion.
  • the present invention relates to a new process aimed at the synthesis of compounds (I) in a single step and with high yields.
  • the process of the invention concerns more specifically the dimerisation of glyoxals (II).
  • an alkaline salt of the hydroxymethanesulfinic acid in the presence of a specific pH conditions, is able to promote the reductive dimerisation of glyoxals (II).
  • R 1 represents a linear or branched Ci to C 5 alkyl group, comprising the dimerisation, in a water-based reaction medium, of a glyoxal of formula
  • R 1 has the same meaning as defined above, said process being characterized in that the dimerisation is carried out a) in the presence of alkaline salt of the hydroxymethanesulfinic acid (i.e. a compound of formula HOCH 2 SO 2 M, M being an alkaline metal ion); and b) in that the pH of the reaction medium is comprised between 3.5 and 9.5.
  • alkaline salt of the hydroxymethanesulfinic acid i.e. a compound of formula HOCH 2 SO 2 M, M being an alkaline metal ion
  • the starting glyoxal (II) is methyl glyoxal, which provides the preferred final dihydroxy-dione (I), namely the 3,4- dihydroxy-hexane-2,5-dione.
  • the preferred alkaline salt of the hydroxymethanesulfinic acid is HOCH 2 SO 2 Na-2H 2 O, also known as Rongalit ® (origin : BASF, Germany).
  • Said salt of the hydroxymethanesulfinic acid can be used in the invention's process in the form of a chemical previously prepared and isolated or can be prepared in situ in the reaction medium, without isolation or purification, just before their use.
  • the experimental procedure for its preparation is substantially similar in both cases and is well known by a person skilled in the art.
  • the use of a salt of the hydroxymethanesulfinic in the form of a pre-isolated compound represents a preferred embodiment.
  • water-based reaction medium it is meant here the medium wherein the reaction takes place, said medium containing at least 50 % of water, percentage being relative to its own weight.
  • a particularly suitable water-based reaction medium is water.
  • the present process is preferably carried out in a reaction medium having a pH comprised between 4.0 and 9.5, preferably between 5.0 and 9.0, more preferably between 5.0 and 7.5.
  • Said buffering salts are derivatives of weak bases or weak acids, and according to an embodiment of the invention they are selected from the group consisting of the alkaline or alkaline-earth carbonates, the alkaline bicarbonates or the mono alkaline phosphates.
  • the buffering salt is selected from the group consisting OfNa 2 CO 3 , CaCO 3 and NaHCO 3 .
  • HOCH 2 SO 2 M is equal to 2. However we have discovered that an excess of HOCH 2 SO 2 M increases the yield of the process. Therefore, according to an embodiment of the invention, a molar ratio Glyoxal (Hy(HOCH 2 SO 2 M) ranging between 2 and 0.3, or between 1.5 and 0.5, can be used advantageously.
  • the temperature at which the process of the invention can be carried out is comprised between 0 0 C and 100 0 C, more preferably between 20 0 C and 6O 0 C.
  • Rongalit ® calcium carbonate and methyl glyoxal (techn. ⁇ 40% in water) are all commercially available from FLUKA (Switzerland).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne le domaine de la synthèse organique et plus spécifiquement un nouveau procédé de dimérisation de glyoxals alkyliques, ce procédé étant favorisé par un sel alcalin de l'acide hydroxyméthanesulfinique et mise en oeuvre à un pH compris entre 3,5 et 9,5.
PCT/IB2005/053489 2004-11-02 2005-10-25 Nouveau procede de dimerisation de glyoxals alkyliques Ceased WO2006048792A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2007539665A JP2008519027A (ja) 2004-11-02 2005-10-25 アルキルグリオキサールの二量体化のための新規方法
EP05796277A EP1812369A1 (fr) 2004-11-02 2005-10-25 Nouveau procede de dimerisation de glyoxals alkyliques
US11/692,809 US7345206B2 (en) 2004-11-02 2007-03-28 Process for the dimerisation of alkyl glyoxals

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IBPCT/IB2004/003636 2004-11-02
IB2004003636 2004-11-02

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/692,809 Continuation US7345206B2 (en) 2004-11-02 2007-03-28 Process for the dimerisation of alkyl glyoxals

Publications (1)

Publication Number Publication Date
WO2006048792A1 true WO2006048792A1 (fr) 2006-05-11

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2005/053489 Ceased WO2006048792A1 (fr) 2004-11-02 2005-10-25 Nouveau procede de dimerisation de glyoxals alkyliques

Country Status (5)

Country Link
US (1) US7345206B2 (fr)
EP (1) EP1812369A1 (fr)
JP (1) JP2008519027A (fr)
CN (1) CN101039895A (fr)
WO (1) WO2006048792A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102452915B (zh) * 2011-05-20 2014-07-09 上海万香日化有限公司 3,4-二羟基-2,5-己二酮的制备方法
CN109879742A (zh) * 2019-03-23 2019-06-14 安徽金禾实业股份有限公司 一种3,4-二羟基-2,5-己二酮的制备方法
CN110845313A (zh) * 2019-09-27 2020-02-28 厦门欧米克生物科技有限公司 一种3,4-二羟基-2,5-己二酮的连续制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3558714A (en) * 1967-06-16 1971-01-26 Firmenich & Cie Process for the preparation of hexane-3,4-diol-2,5-dione

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3837954A1 (de) 1988-11-09 1990-05-10 Basf Ag Verfahren zur herstellung von dihydroxydionen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3558714A (en) * 1967-06-16 1971-01-26 Firmenich & Cie Process for the preparation of hexane-3,4-diol-2,5-dione

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FUSON R C ET AL: "1,2-DIACYLETHYLENE GLYCOLS", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, AMERICAN CHEMICAL SOCIETY, WASHINGTON, DC, US, vol. 61, July 1939 (1939-07-01), pages 3246 - 3249, XP001021797, ISSN: 0002-7863 *

Also Published As

Publication number Publication date
JP2008519027A (ja) 2008-06-05
CN101039895A (zh) 2007-09-19
EP1812369A1 (fr) 2007-08-01
US20070185352A1 (en) 2007-08-09
US7345206B2 (en) 2008-03-18

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